Perturbation of fluorescence by nonspecific interactions between anionic poly(phenylenevinylene)s and proteins: implications for biosensors

The use of anionic water-soluble conjugated polymers (CPs) for sensing the presence of avidin by use of a biotin-modified fluorescence quencher was studied. The molecules involved in the study included poly[2-methoxy-5-(3'-propyloxysulfonate)-1,4-phenylenevinylene] with either lithium (Li+-MPS-PPV) or sodium (Na(+)-MPS-PPV) countercations, the well-defined oligomer pentasodium 1,4-bis(4'(2",4"-bis(butoxysulfonate)-styryl)-styryl)2-butoxysulfonate-5-methoxybenzene (5R5-), the quenchers N-methyl-4,4'-pyridylpyridinium iodide (mMV+) and [N-(biotinoyl)-N'-(acetyl 4,4'-pyridylpyridinium iodide)] ethylenediamine (BPP+), which contains a molecular recognition fragment (biotin) attached to a unit that accepts an electron from a CP excited state, and the proteins avidin, tau, BSA, and pepsin A. Fluorescence quenching experiments were examined in a variety of conditions. Experiments carried out in water and in ammonium carbonate buffer (which ensures avidin/biotin complexation) reveal that nonspecific interactions between the CP and the proteins cause substantial perturbations on the CP fluorescence. The overall findings are not consistent with a simple mechanism whereby avidin complexation of BPP+ leads to encapsulation of the quencher molecule and recovery of Li+-MPS-PPV fluorescence. Instead, we propose that binding of BPP+ to avidin results in the quenching unit attaching to a positively charged macromolecule. Electrostatic attraction to the negatively charged conjugated polymer results in closer proximity to the quencher. Therefore, more enhanced fluorescence quenching is observed.     

Loss measurement of plasmonic modes in planar metal-insulator-metal waveguides by an attenuated total reflection method

We report experimental excitation and characterization of surface plasmon modes in planar metal-insulator-metal (MIM) waveguides. Our approach is based on determining the width of the reflection angular spectrum in the attenuated total reflection (ATR) configuration. Owing to its transverse character, the ATR configuration provides a more straightforward and simpler way to determine the loss of plasmonic modes in MIM structures, compared to using tapered end couplers with multiple waveguide samples or scanning near-field optical microscopy. In this Letter, two waveguide structures with Au claddings and 50/200 nm SiO(2) cores are investigated. The propagation lengths measured at λ = 1.55 μm are 5.7 and 18 μm, respectively, in agreement with the theoretical predictions.     

Donor-Acceptor-Gleichgewichte bei der Copolymerisation. 44. Mitt. Copolymerisation von Styrol und α-Methylstyrol mit Acrylaten und (α-substituierten Acrylaten mit Al-Verbindungen

Ohne Zusammenfassung     

Digital processing capabilities using holographically recorded data pages in electro-optic crystals

Digital logic operations on holographically recorded binary data pages in electro-optic crystals as previously reported by others are summarized and extended. The basic logic operations available and processing capabilities are identified and discussed.     

The variation of spectroscopic properties with numbers of electrons

A formalism that describes the variation of the spectroscopic properties, D_e, R_e, and k_e, of homonuclear, diatomic molecules, with the number of molecular electrons has been developed. The theory describes the interrelation of these properties and predicts “critical” behavior in sequences of “isonuclear” and neutral molecules. Detailed calculations are possible with the help of experimental data in lieu of a deeper, dynamical theory of molecular behavior with respect to electron number. The present work points the way toward a first-principle's theory. © 1992 John Wiley & Sons, Inc.     

Lewis acid-catalyzed reactions on polystyrene

The action of aluminium halides upon polystyrene was studied as a function of the nature of the reaction medium and of the concentration of catalyst. It was demonstrated that polystyrene undergoes crosslinking, the extent of which is particularly important in chlorinated aliphatic solvents and at high catalyst concentrations. In additions, phenyl rings of the polymer are alkylated and halogenated by the solvent or catalyst. Infrared spectroscopic investigation of the structure of the products indicated that in most cases crosslinking was connected with the formation of 1,4-disubstituted, and eventually 1,2,4-trisubstituted benzenes. In carbon tetrachloride medium, meta substitution was also detected. In products obtained when polystyrene was treated with high amounts of the Lewis acid in CCl₄ medium degrees of substitution even higher than three were probable.     

Cyclo- and cyclized diene polymers. XIII. γ-Ray-initiated polymerization of 1,3-dienes

The γ-ray-initiated polymerization of butadiene, isoprene, and 2,3-dimethylbutadiene-1,3 was carried out at temperatures of 20°C. and ?78°C. Polymers of butadiene and isoprene with mixed linear and cyclic structure were proved to result from the polymerization at ?78°C. A monocyclic structure was found for the 2,3-dimethylbutadiene-1,3 polymers initiated either at ?78°C. or in the thiourea canal complex at 20°C.     

Refractive-index profiling of azimuthally asymmetric optical fibers by microinterferometric optical phase tomography

Accurate nondestructive refractive-index profiling is needed in the modeling, design, and manufacturing of optical fibers and fiber devices. Most profile measurement techniques cannot correctly characterize fibers with small or irregular refractive-index variations over their cross sections. Microinterferometric optical phase tomography (MIOPT) is a technique that allows measurement of fiber refractive-index profiles exhibiting such variations. We present the first demonstration, to our knowledge, of MIOPT. The profile of a polarization-maintaining fiber is measured by MIOPT and shown to be in agreement with (destructive) fiber end-face measurements. MIOPT is also applied to the limiting case of a symmetric single-mode fiber.     

Donor-Acceptor Complexes in Copolymerization. III. Conjugated Diene-Acrylonitrile Copolymerization in the Presence of Metal Halides

The copolymerization of isoprene or butadiene with acrylonitrile in the presence of zinc chloride or ethylaluminum sesquichloride, in the presence or absence of a free radical catalyst, at 30-70°C yields an equimolar, diene-acrylonitrile alternating copolymer containing more than 90% trans-1,4 unsaturation, irrespective of monomer charge. The copolymer results from the homopolymerization of a diene-acrylonitrile…metal halide transoid charge transfer complex. When ZnCl₂ is the electron-accepting metal halide and the polymerization is carried out at temperatures of 50°C and higher or to high conversions, the equimolar copolymer is accompanied by a high acrylonitrile polymer, and in the presence of a radical catalyst, by a normal radical copolymer. In the presence of the organoaluminum halide and in the absence of a radical catalyst, the alternating copolymer is the only product, irrespective of monomer charge. However, in the presence of a radical catalyst and at high acrylonitrile monomer charges, e.g., D/AN = 10/90, the alternating copolymer is accompanied by a normal radical copolymer. The formation of equimolar, alternating copolymer at all monomer ratios and in the absence or presence of a radical catalyst indicates that the (D-AN…MX) charge transfer complex readily undergoes homopolymerization and does not copolymerize with free diene or acrylonitrile or with the AN-AN…MX complex.