Synthesis and Study of a Sulfur Heterocycle Fused p-Phenylene Vinylene Conducting Polymer

Abstract

Poly(benzo[1,2-b:4,5-b′]dithiophene-4,8-diyl vinylene) (1) has been prepared by the pyrolysis of the precursor polymer 2 and studied. Quantum mechanical calculations on the aromatic and quinoid monomers, oligomers and polymers indicate that 1 is a planar aromatic polymer.     

Site‐specific reversible immobilization and purification of His‐tagged protein on poly(2‐acetamidoacrylic acid) hydrogel beads

Ni²⁺‐complexed poly(2‐acetamidoacrylic acid) (PAAA) hydrogel beads were developed for the site‐specific reversible immobilization and purification of the histidine‐tagged green fluorescent protein (His‐tagged GFP). PAAA hydrogel beads were prepared by photopolymerization, and significantly improved mechanical properties of PAAA hydrogel beads were observed in comparison with PAAA hydrogel from our previous study. Confocal laser scanning microscopy was used to determine the binding of His‐tagged GFP to the hydrogel beads in three‐dimensional space. Photoluminescence spectroscopy revealed 89% of binding efficiency of His‐tagged GFP to the Ni²⁺‐PAAA hydrogel beads, 51% of yielding recovery. The maximum binding capacity of His‐tagged GFP was estimated to be 0.45 µg/mg of Ni²⁺‐PAAA hydrogel beads. The recombinant His‐tagged GFP from the soluble fraction of E. coli BL21(DE3) cell lysates was purified with Ni²⁺‐PAAA hydrogel beads. The major advantage of the Ni²⁺‐PAAA hydrogel beads system was simple preparation procedures of producing the matrix, because PAAA hydrogel beads had relatively enhanced mechanical strength than soft hydrogels. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and Properties of Self‐doped Polyaniline with Polycationic Templates via Biocatalysis

The enzyme horseradish peroxidase (HRP) was used to polymerize acid‐functionalized anilines to make self‐doped polymer in the presence of a polycationic template. Anionic templates such as sulfonated polystyrene (SPS) could not function as a suitable template for the polymerization of acid‐functionalized aniline derivatives. Several types of polyelectrolytes were used as templates to observe the structural effects and doping behavior of polyaniline/template complexes. The synthesis is straightforward and the conditions are mild in that the polymerization of conducting polyanilines may be carried out in buffered solutions as high as pH 6, with a stoichiometric amount of hydrogen peroxide and catalytic amount of enzyme. The conductivity of these enzymatically synthesized self‐doped polymers was relatively high without additional doping due to the self‐doping of the acid moieties. The conductivity did not decrease dramatically at pH 3 as is the usual case of unsubstituted HCl‐doped polyaniline and maintained good conductivity even at pH 6. The measured conductivity at pH 4～pH 6 is around 10^?4 S/cm to 10^?6 S/cm.     

Characterizing affinity epitopes between prion protein and β-amyloid using an epitope mapping immunoassay

Cellular prion protein, a membrane protein, is expressed in all mammals. Prion protein is also found in human blood as an anchorless protein, and this protein form is one of the many potential sources of misfolded prion protein replication during transmission. Many studies have suggested that β-amyloid_1–42 oligomer causes neurotoxicity associated with Alzheimer''s disease, which is mediated by the prion protein that acts as a receptor and regulates the hippocampal potentiation. The prevention of the binding of these proteins has been proposed as a possible preventative treatment for Alzheimer''s disease; therefore, a greater understanding of the binding hot-spots between the two molecules is necessary. In this study, the epitope mapping immunoassay was employed to characterize binding epitopes within the prion protein and complementary epitopes in β-amyloid. Residues 23–39 and 93–119 in the prion protein were involved in binding to β-amyloid_1–40 and _1–42, and monomers of this protein interacted with prion protein residues 93–113 and 123–166. Furthermore, β-amyloid antibodies against the C-terminus detected bound β-amyloid_1–42 at residues 23–40, 104–122 and 159–175. β-Amyloid epitopes necessary for the interaction with prion protein were not determined. In conclusion, charged clusters and hydrophobic regions of the prion protein were involved in binding to β-amyloid_1–40 and _1–42. The 3D structure appears to be necessary for β-amyloid to interact with prion protein. In the future, these binding sites may be utilized for 3D structure modeling, as well as for the pharmaceutical intervention of Alzheimer''s disease.     

Fast parallel detection of feline panleukopenia virus DNA by multi‐channel microchip electrophoresis with programmed step electric field strength

A multi‐channel microchip electrophoresis using a programmed step electric field strength (PSEFS) method was investigated for fast parallel detection of feline panleukopenia virus (FPV) DNA. An expanded laser beam, a 10× objective lens, and a charge‐coupled device camera were used to simultaneously detect the separations in three parallel channels using laser‐induced fluorescence detection. The parallel separations of a 100‐bp DNA ladder were demonstrated on the system using a sieving gel matrix of 0.5% poly(ethylene oxide) (M_r = 8 000 000) in the individual channels. In addition, the PSEFS method was also applied for faster DNA separation without loss of resolving power. A DNA size marker, FPV DNA sample, and a negative control were simultaneously analyzed with single‐run and one‐step detection. The FPV DNA was clearly distinguished within 30 s, which was more than 100 times faster than with conventional slab gel electrophoresis. The proposed multi‐channel microchip electrophoresis with PSEFS was demonstrated to be a simple and powerful diagnostic method to analyze multiple disease‐related DNA fragments in parallel with high speed, throughput, and accuracy.     

The Reaction of Ninhydrin with Trimethylbenzenes under Friedel-Crafts Reaction Conditions

The reaction of ninhydrin with 1,2,3- and 1,2,4-trimethylbenzene in the presence of H₂SO₄ or AlCl₃ afforded 2-monoaryl and 2,2-diaryl-1,3-indanedione derivatives as the major products. With 1,3,5-trimethylbenzene as the arene nucleophile, either a reduction product or an indenoindanone derivative was obtained depending upon the catalyst employed in the reaction.     

Designed Synthesis of Well‐Defined Pd@Pt Core–Shell Nanoparticles with Controlled Shell Thickness as Efficient Oxygen Reduction Electrocatalysts

Improving the electrocatalytic activity and durability of Pt‐based catalysts with low Pt content toward the oxygen reduction reaction (ORR) is one of the main challenges in advancing the performance of polymer electrolyte membrane fuel cells (PEMFCs). Herein, a designed synthesis of well‐defined Pd@Pt core–shell nanoparticles (NPs) with a controlled Pt shell thickness of 0.4–1.2 nm by a facile wet chemical method and their electrocatalytic performances for ORR as a function of shell thickness are reported. Pd@Pt NPs with predetermined structural parameters were prepared by in situ heteroepitaxial growth of Pt on as‐synthesized 6 nm Pd NPs without any sacrificial layers and intermediate workup processes, and thus the synthetic procedure for the production of Pd@Pt NPs with well‐defined sizes and shell thicknesses is greatly simplified. The Pt shell thickness could be precisely controlled by adjusting the molar ratio of Pt to Pd. The ORR performance of the Pd@Pt NPs strongly depended on the thickness of their Pt shells. The Pd@Pt NPs with 0.94 nm Pt shells exhibited enhanced specific activity and higher durability compared to other Pd@Pt NPs and commercial Pt/C catalysts. Testing Pd@Pt NPs with 0.94 nm Pt shells in a membrane electrode assembly revealed a single‐cell performance comparable with that of the Pt/C catalyst despite their lower Pt content, that is the present NP catalysts can facilitate low‐cost and high‐efficient applications of PEMFCs.     

Cellulose polymorphism study with sum-frequency-generation (SFG) vibration spectroscopy: identification of exocyclic CH2OH conformation and chain orientation

Sum-frequency-generation (SFG) vibration spectroscopy is a technique only sensitive to functional groups arranged without centrosymmetry. For crystalline cellulose, SFG can detect the C6H₂ and intra-chain hydrogen-bonded OH groups in the crystal. The geometries of these groups are sensitive to the hydrogen bonding network that stabilizes each cellulose polymorph. Therefore, SFG can distinguish cellulose polymorphs (I_β, II, III_I and III_II) which have different conformations of the exocyclic hydroxymethylene group or directionalities of glucan chains. The C6H₂ asymmetric stretching peaks at 2,944 cm^?1 for cellulose I_β and 2,960 cm^?1 for cellulose II, III_I and III_II corresponds to the trans-gauche (tg) and gauche-trans (gt) conformation, respectively. The SFG intensity of the stretch peak of intra-chain hydrogen-bonded O–H group implies that the chain arrangement in cellulose crystal is parallel in I_β and III_I, and antiparallel in II and III_II.     

h-Vectors of matroids and logarithmic concavity

Let M be a matroid on E, representable over a field of characteristic zero. We show that h-vectors of the following simplicial complexes are log-concave:

1.

The matroid complex of independent subsets of E.     

Chrysin Derivative CM1 and Exhibited Anti-Inflammatory Action by Upregulating Toll-Interacting Protein Expression in Lipopolysaccharide-Stimulated RAW264.7 Macrophage Cells

Although our previous study revealed that gamma-irradiated chrysin enhanced anti-inflammatory activity compared to intact chrysin, it remains unclear whether the chrysin derivative, CM1, produced by gamma irradiation, negatively regulates toll-like receptor (TLR) signaling. In this study, we investigated the molecular basis for the downregulation of TLR4 signal transduction by CM1 in macrophages. We initially determined the appropriate concentration of CM1 and found no cellular toxicity below 2 μg/mL. Upon stimulation with lipopolysaccharide (LPS), CM1 modulated LPS-stimulated inflammatory action by suppressing the release of proinflammatory mediators (cytokines TNF-α and IL-6) and nitric oxide (NO) and downregulated the mitogen-activated protein kinase (MAPK) and nuclear factor-κB (NF-κB) signaling pathways. Furthermore, CM1 markedly elevated the expression of the TLR negative regulator toll-interacting protein (Tollip) in dose- and time-dependent manners. LPS-induced expression of cell surface molecules (CD80, CD86, and MHC class I/II), proinflammatory cytokines (TNF-α and IL-6), COX-2, and iNOS-mediated NO were inhibited by CM1; these effects were prevented by the knockdown of Tollip expression. Additionally, CM1 did not affect the downregulation of LPS-induced expression of MAPKs and NF-κB signaling in Tollip-downregulated cells. These findings provide insight into effective therapeutic intervention of inflammatory disease by increasing the understanding of the negative regulation of TLR signaling induced by CM1.