LSPR Biosensor Signal Enhancement Using Nanoparticle-Antibody Conjugates

A method to amplify the wavelength shift observed from localized surface plasmon resonance (LSPR) bioassays is developed using gold nanoparticle-labeled antibodies. The technique, which involves detecting surface-bound analytes using gold nanoparticle conjugated antibodies, provides a way to enhance LSPR shifts for more sensitive detection of low-concentration analytes. Using the biotin and antibiotin binding pair as a model, we demonstrate up to a 400% amplification of the shift upon antibody binding to analyte. In addition, the antibody-nanoparticle conjugate improves the observed binding constant by 2 orders of magnitude, and the limit of detection by nearly 3 orders of magnitude. This amplification strategy provides a way to improve the sensitivity of plasmon-based bioassays, paving the way for single molecule-based detection and clinically relevant diagnostics.     

素理想完全分裂的一个判别法则

本文给出了数域K内一个素理想在K的有限次正规扩域L内完全分裂的一个判别法则。     

The general linear model and the generalized singular value decomposition

A new derivation is given for the generalized singular value decomposition of two matrices X and F having the same number of rows. It is shown how this decomposition reveals the structure of the general Gauss-Markov linear model (y, Xβ, σ²FF′), and exhibits the structure and solution of the generalized linear least squares problem used to provide the best linear unbiased estimator for the model. The decomposition is used to prove optimality of the estimator and to reveal the structure of the covariance matrix of the error of the estimator.     

Activation/driving force relationships for cyclopropylcarbinyl --> homoallyl-type rearrangements of radical anions

By using direct and indirect electrochemical methods, rate constants (ko) for cyclopropane ring opening of radical anions derived from the one-electron reduction of trans-1-benzoyl-2-phenylcyclopropane, trans-1-benzoyl-2-vinylcyclopropane, 2-methylenecyclopropyl phenyl ketone, spiro[anthracene-9,1'-cyclopropan-10-one], 3-cyclopropylcyclohex-2-en-1-one, and 3-(1-methylcyclopropyl)cyclohex-2-en-1-one were determined. Qualitatively, rate constants for ring opening of these (and other cyclopropyl- and cyclobutyl-containing radical anions) can be rationalized on the basis of the thermodynamic stability of the radical anion, the ability of substituents on the cyclopropyl group to stabilize the radical portion of the distonic radical anion, and the stability of the enolate portion of the distonic radical anion. On the basis of this notion, a thermochemical cycle for estimating deltaG(o) for ring opening was presented. For simple cyclopropyl-containing ketyl anions, a reasonable correlation between log(ko) and deltaG(o) was found, and stepwise dissociative electron transfer theory was applied to rationalize the results. Activation energies calculated with density functional theory (UB3LYP/6-31+G*) correlate reasonably well with measured log(ko). The derived log(ko) and deltaG(o) and log(ko) vs E(a) plots provide the basis for a "calibration curve" to predict rate constants for ring opening of radical anions derived from carbonyl compounds, in general.     

Effect of Light on the Electrokinetic Behavior of TiO(2) Particles in Contact with Cr(VI) Aqueous Solutions

The electrokinetic behavior of titanium dioxide particles (Degussa P25, mainly composed of anatase) put in contact with chromium(VI) aqueous solutions is highly sensitive to light exposure under normal laboratory conditions. In the dark, adsorption of Cr(VI) gives rise to substantial decrements in the mobilities, especially in the acidic branch, and, at higher concentrations, to shifts in the isoelectric point (pH(piep)) to lower values, as expected for anionic chemisorption. A two-mode adsorption model accounts qualitatively for the results. Under light, pH(piep) shifts in the opposite direction as the Cr(VI) concentration increases. A maximum value is attained at [Cr(VI)] approximately 10(-3) mol dm(-3), pH(piep) 8.2, which coincides with values reported for hydrous chromium(III) oxides. At higher concentrations, Cr(VI) adsorption defines a shift of pH(piep) to lower values. It is concluded that light absorption by titanium dioxide promotes the reduction of Cr(VI) and the surface precipitation of the hydrous Cr(III) oxide. The values of pH(piep) for partially covered surfaces are well described by a simple model of surface ionization derived earlier. FTIR/ATR analysis of the surfaces supports this interpretation, and further suggests that one of the modes of Cr(VI) adsorption implies surface dimerization to yield adsorbed dichromate. Copyright 2000 Academic Press.     

A Robust, Environmentally Benign Catalyst for Highly Selective Hydroformylation

By a sol-gel process a rhodium complex containing a diphosphane with a large natural P-Rh-P bite angle is covalently anchored in a silica matrix (see picture). The immobilized catalyst is a very selective hydroformylation catalyst that is completely and conveniently separated from the product and can be reused in numerous cycles.     

Sur une propriété des formes algébriques préparées

Sans résumé