0000000000528340
AUTHOR
María-josé Bañuls
ChemInform Abstract: Addition of Organolithium Reagents to Cinnamic Acids.
Abstract Reaction of tert -butyllithium with p - and m -substituted cinnamic acids at low temperature affords mixtures of 1,4- and 1,3-addition products, whose composition depend on the nature of the substituents. Electron-donating and electron-withdrawing groups favour 1,4- and 1,3-additions, respectively. Linear correlations are obtained with electronic effect and with radical substituent constants.
Modeling of the role of conformational dynamics in kinetics of the antigen-antibody interaction in heterogeneous phase.
[EN] A novel approach that may potentially be used to study biomolecular interactions including the simultaneous determination of structural and kinetic binding parameters is described in this Article for the first time. It allows a rigid distinction between the possible reaction mechanisms of biomolecular recognition, induced fit and conformational selection. The relative importance of the two pathways is determined not by comparing rate constants but the structural aspects of the interaction instead. So the exact location of antigen molecules with respect to the capture antibody is depicted experimentally, avoiding the use of X-ray crystallography. The proposed pattern is applied to study…
Addition of organolithium reagents to cinnamic acids
Abstract Reaction of tert -butyllithium with p - and m -substituted cinnamic acids at low temperature affords mixtures of 1,4- and 1,3-addition products, whose composition depend on the nature of the substituents. Electron-donating and electron-withdrawing groups favour 1,4- and 1,3-additions, respectively. Linear correlations are obtained with electronic effect and with radical substituent constants.
Magnetoelectrochemical modulation of pre-organization processes in a 4,4′-dinitrobiphenyl azacrown macrocyclic lactam
A magnetoelectrochemical effect consisting on the modulation of the reaction rate of pre-organization reactions in a 4,4′-dinitrobiphenyl azacrown lactam is described. The electrochemical response of that compound in DMSO solution at microelectrodes consists in two successive dinitrobiphenyl-centred one-electron transfer processes at −0.9 and −1.6 V vs. AgCl/Ag involving the transition from the dihedral geometry of the neutral starting compound to the planar geometry of the final dianion, resulting in an overall ECE mechanism. In the presence of moderate (0.05–0.2 T) static magnetic fields, the second electron transfer process decreases significantly, the apparent rate constant of the dihed…
Experimental Study of the Oriented Immobilization of Antibodies on Photonic Sensing Structures by Using Protein A as an Intermediate Layer
[EN] A proper antibody immobilization on a biosensor is a crucial step in order to obtain a high sensitivity to be able to detect low target analyte concentrations. In this paper, we present an experimental study of the immobilization process of antibodies as bioreceptors on a photonic ring resonator sensor. A protein A intermediate layer was created on the sensor surface in order to obtain an oriented immobilization of the antibodies, which enhances the interaction with the target antigens to be detected. The anti-bovine serum albumin (antiBSA)-bovine serum albumin (BSA) pair was used as a model for our study. An opto-fluidic setup was developed in order to flow the different reagents and,…
On the mechanism of the addition of organolithium reagents to cinnamic acids
Abstract The regioselectivity of the addition of tert-butyllithium to cinnamic acid is subject to reaction conditions and to substituent electronic effects. Significant effects are observed in the presence of several additives including a radical trap such as α-methylstyrene. Competition experiments by addition of the organolithium reagent to mixtures of substituted cinnamic acids show that the relative rates of both conversion of the starting acids and formation of the 1,3-adducts are subject to electronic effects, whereas rates for 1,4-addition are independent of the substituents. These features are in agreement with a polar addition mechanism, but a fast SET equilibrium followed by slow …
Magnetoelectrochemistry of 4,4′-bis(dimethylamino)biphenyl and 4,4′-dinitrobiphenyl azacrown macrocyclic lactams
Abstract The voltammetric behaviour at carbon fibre microelectrodes under the application of static magnetic fields of two series of macrolactams containing in their structure 4,4′-bis(dimethylamino)biphenyl or 4,4′-dinitrobiphenyl groups in MeCN solution is described. The response of 4,4′-dinitrobiphenyl receptors is dominated by two successive one-electron reduction processes at −0.9 and −1.6 V versus AgCl/Ag. 4,4′-bis(dimethylamino)biphenyl-containing receptors display two one-electron oxidations above +0.8 and +1.0 V. In both cases, a dihedral/planar interconversion precedes the second electron transfer step. Upon application of moderate (0.05–0.2 T) static magnetic fields to the electr…