某些多氮杂大环的合成与应用

多氮杂大环与许多金属离子能形成稳定的络合物。由于氮原子是三价的,因而多氮杂大环比冠醚具有更有利的结构;如果再导入羧基、膦酸基以及其他的亲水基团,则可得到一系列能形成水溶性金属络合物的配体。其中某些金属(如铜、钇等)的络合物在人体生理条件下表现出很好的稳定性,结合单原抗体技术的应用,这炎络合物在医疗、诊断方面有实用性。本文简单介绍某些代表性络合物的制备方法、物理性能和可能的应用。     

Influence of the preparation procedure on the properties of polyaniline based magnetic composites

A versatile process for the preparation of composite films consisting of magnetite (Fe₃O₄) nanoparticles embedded in a polyaniline (PANI) matrix is reported. Spectroscopic properties of polyaniline matrix (PANI-EB), polyaniline protonated with camphor sulfonic acid (PANI-CSA_0.5) PANI-ES and PANI/Fe₃O₄-CSA_0.5 composites were studied, both in the state of the solutions of m-cresol and in thin films processed from the same solvents. The results of these studies indicate that m-cresol can be used for PANI/Fe₃O₄ composite preparation. Such films show both reasonably high electrical conductivity and magnetic permeability. A controlled application of a magnetic field during the casting process resulted in the formation of the materials with an unusual combination of magnetic and transport properties. The obtained films show the behavior that can be explained by the presence of both ferromagnetic and paramagnetic phases. The superparamagnetic contribution, if any, is very small. Application of the external magnetic field during fabrication of the composites stimulates creation of the aggregates of magnetic particles which, although keeps conductivity at a relatively high level, leads to a small decrease of the conductivity value.     

Heat transfer from a rarefied plasma flow to a metallic or nonmetallic particle

Heat transfer from a plasma flow to a metallic or nonmetallic spherical particle is studied in this paper for the extreme case of free-molecule flow regime. Analytical expressions are derived for the heat flux due to, respectively, atoms, ions, and electrons and for the floating potential on the sphere exposed to a two-temperature plasma flow. It has been shown that the local or average heat flux density over the whole sphere is independent of the sphere radius and approximately in direct proportion to the gas pressure. The presence of a macroscopic relative velocity between the plasma and the sphere causes substantially nonuniform distributions of the local heat flux and enhances the total heat flux to the sphere. The heat flux is also enhanced by the gas ionization. Appreciable difference between metallic and nonmetallic spheres is found in the distributions along the oncoming flow direction of the floating potential and of the local heat flux densities due to ions and electrons. The total heat flux to the whole sphere is, however, almost the same for these different spheres. For a fixed value of the electron temperature, the heat flux decreases with increasing temperature ratio T_e/T_h.     

Equilibrium of the reaction between dissolved sodium sulfide and biologically produced sulfur

The equilibrium of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied. Biologically produced sulfur was obtained from a bioreactor of a hydrogen sulfide removal process in which the dominating organism is Thiobacillus sp. W5. Detailed knowledge of this reaction is essential to understand its effect on the process. The results were compared with the equilibrium of the reaction of sulfide with ‘inorganic’ elemental sulfur. The equilibrium between dissolved sodium sulfide and biologically produced sulfur particles can be described by an equilibrium constant, K_x, which consists of a weighted sum of constants for polysulfide ions of different chain length, rather than a true single equilibrium constant. For biologically produced sulfur pK_x = 9.10 ± 0.08 (21 °C) and 9.17 ± 0.09 (35 °C) with an average polysulfide chain length x = 4.91 ± 0.32 (21 °C) and 4.59 ± 0.31 (35 °C). The pK_x value for biologically produced sulfur is significantly higher than for reaction of dissolved sodium sulfide with inorganic sulfur (pK_x = 8.82; 21 °C). This difference is probably caused by the negatively charged polymeric organic layer, which is present on biologically produced sulfur but absent with “inorganic” sulfur. Specific binding of polysulfide ions to the organic layer results in a higher polysulfide concentration at the reaction site compared to the bulk concentration. This results in an apparent decrease of the measured equilibrium constant, K_x.     

Dispersion polymerization of methyl methacrylate: Mechanism of particle formation

The mechanism for the formation of micron-size polymer particles in the dispersion polymerization of methyl methacrylate was investigated by applying dynamic light scattering to monitor the evolution of the average particle size in the early stages of the polymerization. In addition, the contributions of physically adsorbed stabilizer and graft copolymer were evaluated by measuring the bound, unbound (adsorbed), and free stabilizer, and by determining the amount of added stabilizer required in seeded dispersion polymerizations. Twenty nanometer particles (termed nuclei) were the smallest particles detected and are considered to be formed by aggregation of growing polymer chains precipitating from solution as they exceed their critical chain length. Aggregation of these nuclei with themselves and their aggregates continues until mature and stable particles are formed. This occurs when sufficient stabilizer occupies the particle surface which includes both the polymeric stabilizer [poly(vinylpyrrolidone)] and its graft copolymer which is created in situ. The effects of process variables are discussed based on this mechanistic picture of the dispersion polymerization process. © 1994 John Wiley & Sons, Inc.     

Chemical modification of silica surface by immobilization of functional groups for extractive concentration of metal ions

Increased utilization of mechanically stable synthetic matrices particularly silica gel as a solid support and its surface modification either by impregnation of organic ligands directly or covalent grafting through spacer unit for extractive concentration of trace elements are highlighted in the present article. Experimental evidences for existence of surface silanol and its chemical nature have explored the idea of silica surface modification. Recent methods of development in functionalized silica synthesis by attachment of various ligands or organic reagents to the silica surface and techniques of characterization of the modified surface have been reported. Analytical applications of various modified silica surfaces, in particular, adsorption of trace elements taking separation and preconcentration into account from complex synthetic mixture as well as natural water is presented.     

Synthesis, characterization and potential biomedical applications of N-succinimidyl ester functionalized, polypyrrole-coated polystyrene latex particles

N-Succinimidyl ester functionalized polypyrrole-coated polystyrene latex particles (PS_E-PPyNSE) were prepared by the in situ copolymerization of pyrrole and the active ester-functionalized pyrrole (pyrrole-NSE) in the presence of polystyrene latex particles. Polystyrene microspheres were prepared by emulsion polymerization (PS_E) leading to particles having a diameter of 450 nm. These PS_E particles were precoated with poly(N-vinylpyrrolidone) prior to the in situ copolymerization of pyrrole and pyrrole-NSE. The initial comonomer concentration fractions were 25/75, 50/50 and 75/25 for pyrrole and pyrrole-NSE, respectively. The PPy-coated PS_E particles were characterized in terms of morphology, particle size, electrophoretic mobility and chemical composition. The study of morphology by means of scanning electron microscopy showed roughening of the underlying PS_E particles owing to the addition of PPyNSE, the overlayer thickness of which was estimated to be around 7 nm. Moreover, loading PPyNSE overlayers resulted in a shift of the electrophoretic mobility from –5.31 m cm/V s to a very small but positive value (0.082–0.112 m cm/V s). X-ray photoelectron spectroscopy and IR spectroscopy permitted the detection of pyrrole-NSE repeat units at the surface indicating that pyrrole and pyrrole-NSE did indeed copolymerize. The PS_E-PPyNSE particles were further evaluated as bioadsorbents of human serum albumin used as a test protein. For this study, PS_E-PPyNSE₅₀ particles, synthesized from a comonomer feed ratio of 50/50 in pyrrole/pyrrole-NSE, were used and were shown to attach efficiently human serum albumin macromolecules with a maximum amount of 0.2 mg m^–2.

Metal Oxide Film Anodes in the Electrolysis of Water or Brine

Metal (M) oxide (M: Ir, Os, Pd, Pt, Rh, Ru) together with MaO₂ and MnO₂ alone, were coated on SnO₂ films and the anode behavior was examined in 1.0 N H₂SO₄, 1.0 N NaOH and 1.0, N NaCl aqueous solutions at 25°. The results are compared with those of DSA and of metallic Pt.     

NRET from naphthalene labels in multilayer shell wall on melamine formaldehyde microparticles fabricated with layer-by-layer self-assembly to pyrene-labeled polyelectrolyte in solution

Core-shell colloidal particles were prepared with the core of monodisperse melamine formaldehyde particles (MF) with a diameter of 3.5 μm. The shell deposited on the core by the layer-by-layer (LbL) self-assembly was made with a copolymer ANp3 of 2-acrylamido-2-methylpropanesulfonate sodium (AMPS) and 3 mol% naphthalene label monomer and poly(diallyldimethylammonium chloride) (PD). Nonradiative energy transfer (NRET) from the naphthalene labels deposited on the MF particles to pyrene labels at a polyelectrolyte APy3, a copolymer of AMPS and 3 mol% pyrene label monomer, or to an ionic pyrene probe 1-pyrenemethylamine hydrochloride (PyMeA · HCl) in water was observed. The NRET efficiency was expressed as the emission intensity ratio I/I₀ of naphthalene with and without existence of pyrene in the surrounding solution. With increasing pyrene concentration, I/I₀ decreased down to about 0.2 and the mechanism for this NRET from the inner naphthalene label to the pyrene labels in solution is still ambiguous.     

Nitrotyrosine-modified proteins and oxidative stress induced by diesel exhaust particles

Protein tyrosine nitration is a post-translational modification that occurs under conditions of oxidative stress and may play a role in the pathogenesis of diseases such as asthma. Through their ability to generate reactive oxygen species in macrophages and epithelial cells, particulate pollutants, such as diesel exhaust particles (DEPs), may lead to a worsening of the asthmatic condition. In this study, we looked for evidence of oxidative modification of proteins in RAW 264.7 cell line treated with DEP chemicals. We show that the induction of oxidative stress is accompanied by 53 newly expressed proteins which are suppressed by a thiol antioxidant, N-acetylcysteine. These include antioxidant enzymes, pro-inflammatory components, and products of intermediary metabolism. In addition, inducible nitric oxide synthase (iNOS) was identified as a biologically relevant oxidative stress protein that is induced concurrent with increased NO production and protein tyrosine-nitration in DEP-exposed RAW 264.7 cells. Utilizing two-dimensional gel electrophoresis, anti-nitrotyrosine immunoblotting, and mass spectrometry led to the identification of an additional ten nitrotyrosine modified proteins, including oxidative stress proteins involved in intermediary metabolism (e.g., GAPDH and enolase), antioxidant defense (e.g., MnSOD) and inhibition of proteosomal activity (e.g., Hsp 90alpha). These oxidative proteins may serve as markers for oxidative stress generation in vivo.