Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Viscosity,particle size distribution,and structural investigation of tetramethyloxysilane/2‐hydroxyethyl methacrylate sols during the sol–gel process with acid and base catalysts

The tetramethoxysilane (TMOS)/2‐hydroxylethyl methacrylate (HEMA) hybrid gels were synthesized with acid and base catalysts, via the in situ polymerization of HEMA, with and without the cosolvent methanol. With methanol in the TMOS/HEMA sol, the enhanced esterification and depolymerization reactions of the silanols resulted in a slower growth of silica particles. The silica particles that were synthesized with an acid catalyst were less than 40 nm. The thermal resistance of the poly(2‐hydroxyethyl methacrylate) (PHEMA) chains was enhanced by the addition of colloidal silica. The Fourier transform infrared characterizations and the exothermal peaks on the differential scanning calorimetry traces of these hybrid gels indicated chemical hybridization occurring as a result of condensation of the colloid silica and PHEMA at higher temperatures. Hence, the residual weight content of the hybrid gel after its synthesis with the base catalyst was even higher than the content of TMOS in the hybrid sol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3476–3486, 2004     

Ferritin immunosensing on microfabricated electrodes based on the integration of immunoprecipitation and electrochemical signaling reactions.

A signal registration strategy from micropatterned immunosensors that converts antigen-antibody binding reactions into electrochemical signals was demonstrated. An array-type micropatterned gold electrode on a silicon wafer was fabricated, containing two electrode geometries of rectangular (100 microm x 500 microm) and circular (r. 50 microm) types, exhibiting electrochemical characteristics of bulk and micro-electrodes, respectively. Ferritin was employed as a model analyte for immunosensing because it has an advantageous molecular structure for functionalization to the sensing interface, and is regarded as a general marker protein for tumors and cancer recurrence. With the fabricated and ferritin-functionalized immunosensors, biospecific interactions were performed with antiferritin antiserum and secondary antibody samples, followed by electrochemical signaling via an immunoprecipitation reaction by the label enzyme. Under the optimized affinity-surface construction steps and reaction conditions, both types of microfabricated electrodes exhibited well-defined calibration results as a function of the protein concentration in antiserum samples. Furthermore, circular-type micropatterned immunoelectrodes exhibited voltammetric characteristics of microelectrodes, which is advantageous in terms of sensor operation under a fixed potential and low signal drift during the signaling reaction compared with the bulk-type electrodes. The results support that the employed signaling method with the proposed immunosensor configuration is fit for sensor miniaturization and integration to future biomicrosystems.     

Fluorescent-based single-strand conformation polymorphism/heteroduplex capillary electrophoretic mutation analysis of the P53 gene.

Fluorescent-based single-strand conformation polymorphism (F-SSCP) analysis with capillary electrophoresis (CE) is the most common method for the detection of mutation because of its high sensitivity and resolution. In this study, we prepared an inexpensive linear polyacrylamide (LPA), and successfully applied it to CE-SSCP analysis and tandem CE-SSCP/heteroduplex analysis (HA) of the P53 gene on an ABI capillary genetic analyzer. A comparison of the sieving capabilities of a homemade LPA and commercial polydimethylacrylamide (PDMA) demonstrates that the homemade LPA has a higher resolution, a shorter analysis time, and is more suitable for tandem SSCP/HA than commercial PDMA. To show the usefulness, mutations of P53 gene exon 7 - 8 in 37 tumor samples were investigated by using homemade LPA. The results indicate that 10 mutations were found in 9 of 37 cases; the majority of P53 mutations were missense mutations, and 70% were located in exon 7, which plays an important role in neoplastic progression in human tumorigenesis.     

Ba（n，x）~（134）Cs，~（134）Ba（n，2n）~（133）Ba，

用中子活化法相对于５４Ｆｅ（ｎ，Ｐ）５４Ｍｎ反应，在１３．５０—１４．８０ＭｅＶ中子能区测量了Ｂａ（ｎ，ｘ）１３４Ｃｓ，１３４Ｂａ（ｎ，２ｎ）１３３Ｂａ，１４０Ｃｅ（ｎ，２ｎ）１３９Ｃｅ，１４２Ｃｅ（ｎ，２ｎ）１４１Ｃｅ和２３Ｎａ（ｎ，２ｎ）２２Ｎａ的反应截面．并将所测的结果和其他作者的结果进行了比较，中子能量是用９０Ｚｒ（ｎ，２ｎ）８９ｍ＋ｇＺｒ反应和９３Ｎｂ（ｎ，２ｎ）９２ｍＮｂ反应截面比法测定的。     

Optical behaviour of photoimageable cholesteric liquid crystal cells with various novel chiral compounds

In theory, both polarity and steric hindrance are basic factors which affect molecular interactions. To investigate the optical properties and steric structures of chiral compounds having different chiral moieties which affect the wavelength of light reflection in liquid crystal (LC) cells, a series of novel chiral compounds and azobenzene derivatives were synthesized. The liquid crystalline phases of the compounds were identified using small angle X-ray diffraction, differential scanning calorimetry and polarizing optical microscopy. Cholesteric LC cells with various synthesized chiral dopants which selectively reflect visible light were first prepared, the photochemical switching behaviour of colours was then investigated, with special reference to the change in transmittance in cholesteric LC cells containing an azobenzene derivative as a photoisomerizable guest molecule. Reversible isomerization of azobenzene molecules occurred in the cholesteric systems, resulting in a depression of T_ChI and a shift of the selectively reflected wavelength. We discuss the photochemically driven change in the helical pitch of the cholesteric LCs with respect to structural effects involving the chiral moieties. Molecular interactions caused by the added dopants, reliability and stability of the photoisomerization, and UV irradiation effects on the cholesteric LC cells were also investigated. A real image was recorded through a mask on a cholesteric LC cell fabricated in this investigation.     

A complete boundary integral formulation for compressible Navier–Stokes equations

A complete boundary integral formulation for compressible Navier–Stokes equations with time discretization by operator splitting is developed using the fundamental solutions of the Helmholtz operator equation with different order. The numerical results for wall pressure and wall skin friction of two‐dimensional compressible laminar viscous flow around airfoils are in good agreement with field numerical methods. Copyright © 2004 John Wiley & Sons, Ltd.     

Dispersion and distribution of organically modified montmorillonite in nylon‐66 matrix

Nylon‐66 nanocomposites were prepared by melt‐compounding nylon‐66 with an alkyl ammonium surfactant pretreated montmorillonite (MMT). The thermal stability of the organic MMT powders was measured by thermogravimetric analysis. The decomposition of the surfactant on the MMT occurred from 200 to 500 °C. The low onset decomposition temperature of the organic MMT is one shortcoming when it is used to prepare polymer nanocomposites at high melt‐compounding temperatures. To provide greater property enhancement and better thermal stability of the polymer/MMT nanocomposites, it is necessary to develop MMT modified with more thermally stable surfactants. The dispersion and spatial distribution of the organic MMT layers in the nylon‐66 matrix were characterized by X‐ray diffraction. The organic MMT layers were exfoliated but not randomly dispersed in the nylon‐66 matrix. A model was proposed to describe the spatial distribution of the organic MMT layers in an injection‐molded rectangular bar of nylon‐66/organic MMT nanocomposites. Most organic MMT layers were oriented in the injection‐molding direction. Layers near the four surfaces of the bar were parallel to their corresponding surfaces; whereas those in the bulk differed from the near‐surface layers and rotated themselves about the injection‐molding direction. The influence of the spatial distribution of the organic MMT on crystallization of nylon‐66 was also investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1234–1243, 2003     

Synthesis and characterization of white‐light‐emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9‐hexyl‐9‐(iridium (III)bis(2‐(4′‐fluorophenyl)‐4‐phenylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐PIr) and 9‐hexyl‐9‐(iridium(III)bis(2‐(4′‐fluorophenyl)‐4‐methylquinoline‐N,C^2′)(tetradecanedionate‐11,13))‐2,7‐dibromofluorene (Br‐MIr), were successfully synthesized. The Suzuki polycondensation of 2,7‐bis(trimethylene boronate)‐9,9‐dioctylfluorene with 2,7‐dibromo‐9,9‐dioctylfluorene and Br‐PIr or Br‐MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5–3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue‐ and orange‐emission peaks. A white‐light‐emitting diode with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br‐PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br‐MIr) was employed as the white‐emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants. © 2007 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 45: 1746–1757, 2007     

Influence of preparation methods on structure and properties of PA6/PA66 blends: A comparison of melt‐mixing and in situ blending

The blends composed of polyamide 6 (PA6) and polyamide 66 (PA66) were obtained using two different preparation methods, one of which was the melt‐mixing through a twin‐screw extruder and the subsequent injection molding; and the other, the in situ blending through anionic polymerization of ε‐caprolactam in the presence of PA66. For the former, there existed a remarkable improvement in toughness but a drastic drop in strength and modulus; however, for the latter, a reverse but less significant trend of mechanical properties change appeared. Various characterizations were conducted, including the analyses of crystalline morphology, crystallographic form, and crystallization and melting behaviors using polarized optical microscopy (POM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC), respectively; observation of morphology of fractured surface with scanning electron microscope (SEM); measurement of glass transition through dynamic mechanical analysis (DMA); and the intermolecular interaction as well as the interchange reaction between the two components by Fourier transform infrared spectrometry (FT‐IR) and ¹³C solution NMR. The presence and absence of interchange reaction was verified for the in situ and melt‐mixed blends, respectively. It is believed that the transreaction resulted in a drop in glass transition temperature (T_g) for the in situ blends, contrary to an increase of T_g with increasing PA66 content for the melt‐mixed ones. And the two kinds of fabrication methods led to significant differences in the crystallographic form, spherulite size and crystalline content and perfection as well. Accordingly, it is attempted to explain the reasons for the opposite trends of changes in the mechanical properties for these two blends. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1176–1186, 2007