Liposomes as signal amplification reagents for bioassays in microfluidic channels

Liposomes with encapsulated carboxyfluorescein were used in an affinity-based assay to provide signal amplification for small-volume fluorescence measurements. Microfluidic channels were fabricated by imprinting in a plastic substrate material, poly(ethylene terephthalate glycol) (PETG), using a silicon template imprinting tool. Streptavidin was linked to the surface through biotinylated-protein for effective immobilization with minimal nonspecific adsorption of the liposome reagent. Lipids derivatized with biotin were incorporated into the liposome membrane to make the liposomes reactive for affinity assays. Specific binding of the liposomes to microchannel walls, dependence of binding on incubation time, and nonspecific adsorption of the liposome reagent were evaluated. The results of a competitive assay employing liposomes in the microchannels are presented.     

Substitution and condensation reactions with poly(anilineboronic acid): reactivity and characterization of thin films

Poly(anilineboronic acid) thin films are treated under various conditions to achieve substitution or condensation reactions involving the boronic acid moiety. These reactions are studied with polarization modulated infrared reflection absorption spectroscopy, cyclic voltammetry, and UV-vis spectroscopy. The results suggest the single-step formation of substituted polyanilines, such as poly(hydroxyaniline), halogenated polyanilines, and mercury chloride-substituted polyaniline. A condensation reaction of poly(anilineboronic acid) with cis-diol compounds in aqueous solution, as well as with phenylenebisboronic acid and salycilamide in THF, indicates the formation of boronic esters. The latter reactions appear to be a good entry point for the formation of complex or supramolecular polymer structures.     

A novel synthetic route to substituted pyranoanthocyanins with unique colour properties

Anthocyanins, isolated from natural sources by countercurrent chromatography, were reacted with cinnamic acids bearing at least one electron-donating substituent at the para-position. The resulting pyranoanthocyanins obtained by this simple one-step reaction were much less susceptible to pH shifts and retained their original colour over a wide pH-range. Through reaction with p-dimethylamino cinnamic acid, synthetic malvidin- and cyanidin-based anthocyanins with a unique violet hue were prepared.     

Effect of Doping and Solution Redox Relays on the Efficiency of Photocathodic Processes at the p-InP/Water Interface

Light-induced interfacial electron transfer from two p-InP electrodes differing in the amount of majority carrier doping to a number of electron relays ( R ) dissolved in aqueous solution was investigated. The material with the lower carrier density (0.71 × 10¹⁸ cm^?3) exhibited much better wavelength response and quantum yield for electron transfer than the electrode doped with 2.3 × 10¹⁸ cm^?3 charge carriers. Using cobalt (III) sepulcrate, Co (sep)³⁺, as an electron relay a polychromatic light to electrical energy conversion efficiency of 18% was obtained. The potential of this relay for use in a regenerative photoelectrochemical cell is briefly discussed.     

Beryllocene, (C5H5)2Be. The He(I) photoelectron spectrum and ab initio molecular orbital calculations

Ab initio molecular orbital calculations with a double-ζ basis have been carrried out on five models of beryllocene, Cp₂Be, with fixed geometries. The lowest energies are obtained for the π-Cp, σ-Cp and D_5d models.

The He(I) photoelectron spectrum of Cp₂Be was recorded and the ionization potentials of the first bands were compared with the orbital energies obtained from the molecular orbital calculations. A satisfactory fit between experiment and calculations was obtained for a slip sandwich model of C_s symmetry. A model of C_5v symmetry is only compatible with the PE spectrum if the Jahn—Teller splitting of the lowest ²E₁ state of the molecular ion is exceptionally large, 1.0 eV.     

A Green's function approach to the photoelectron spectrum of bis(π-allyl)nickel[1]

The vertical ionization potentials of bis(-allyl)nickel (see (1) in Fig. 1) are calculated by means of the Green's function approach within a semiempirical INDO extension to the first transition metal series. The computed ionization potentials are in good agreement with an experimentally deduced assignment. In contrast to earlier theoretical and experimental studies, the 7a _u () level is predicted on top of the levels corresponding to the Ni 3d orbitals. Our approach leads to a complete assignment of the PE spectrum of (1) in the outer valence region.     

Some reactions of copper(I) pentafluorothiophenolate as a nucleophile

Several aromatic compounds containing one or two C₆F₅S groups have been prepared by nucleophilic displacement reactions using CuSC₆F₅ in DMF solution. Aromatic iodine or bromine, rather than chlorine of fluorine is replaced by the SC₆F₅ group using CuSC₆F₅. A mechanism is postulated. New compounds prepared include $\text{p}$-(C₆F₆F₅S)₂C₆H₄, $\text{o}$- and $\text{m}$-(C₆F₅S)₂C₆F₄ and $\text{p}$XC₆H₄SC₆F₅(X=C1, NO₂, I, CH₃, CO₂C₂H₅).     

CHEMISTRY OF SINGLET OXYGEN—XXVI. PHOTOOXYGENATION OF PHENOLSy†

Abstract— The aerobic dye-sensitized photooxygenation of monohydric phenols proceeds by way of singlet oxygen under the conditions studied. Various phenols give different proportions of reaction with and quenching of singlet oxygen. Para-substituted 2,6-di-t-butylphenols show a linear correlation between the log of the total rate of singlet oxygen removal and their halfwave oxidation potentials; the same correlation is given for certain phenol methyl ethers. A Hammett plot using s?⁺ gives ρ - 1.72 ± 0.12, consistent with development of some charge in the quenching step. Reaction of photo-chemically generated singlet oxygen with 2,4,6-triphenylphenol gives 2,4,6-triphenylphenoxy radical as an intermediate in singlet oxygen quenching, although no overall reaction occurs. Kinetic analysis indicates that the radical is derived exclusively from the interaction of 2,4,6-triphenylphenol with singlet oxygen. A charge-transfer mechanism for quenching of singlet oxygen by phenols is proposed.     

A CNDO/INDO crystal orbital model for transition metal polymers of the 3d series—basis equations

The crystal orbital formalism in the tight-binding approximation is combined with a recently developed CNDO/INDO model for transition metal species of the 3d series in order to allow band structure calculations on the Hartree-Fock (HF) SCF level for one-dimensional (1D) chains with organometallic unit cells. The band structure approach based on the CNDO and INDO approximation can be used for any atom combination up to bromine under the inclusion of the 3d series. The matrix elements for the tight-binding Hamiltonian are derived for an improved CNDO and INDO framework. The total energy of the 1D chain is partitioned into one-center contributions and into two-center increments of the intracell and intercell type. Semiempirical band structure calculations on simple model systems are compared with available ab initio data of high quality.     

Translational-energy spectroscopy of NO+ and NO2+

High-resolution translational-energy spectroscopy (up to 0.1 eV) has been carried out on 8

V beams of NO^? and NO^2?. Several features in the spectrum of NO⁴ are assigned to the transitions within the triplet manifold of this ion. The observed transitions originate in several excited electronic states, indicating long lifetimes (> 10 μs) for the states involved. Two electronic transitions in NO²' have been observed at low energies which are attributed to excitations to the first two excited states of this ion.