Triarylmethanes and 9-arylxanthenes as prototypes amphihydric compounds for relating the stabilities of cations, anions and radicals by C-H bond cleavage and electron transfer
摘要:
Thermodynamic stability properties of II p-substituted trityl and seven 9-phenylxanthyl carbocations are reported in sulfolane and of their conjugate carbanions in DMSO. The cations are compared by calorimetric heats of hydride transfer from cyanoborohydride ion, their first and second reduction potentials, their PK(R)(+)s in aqueous sulfuric acid, C-13 chemical shifts and free energies of methoxy exchange. Carbanlons are compared by their heats and free energies (pK(HA)) of deprotonation and their first and second oxidation potentials. Radicals are compared by their oxidation and reduction potentials. Their bond dissociation energies are derived by alternative routes: from the carbocation and its reduction potential and from the carbanion and its oxidation potential. The various properties are correlated against each other and against appropriate Hammett-type substituent parameters. Correlations between the different measured properties reported here range from fair to excellent, Despite their importance as historic prototypes for the three trivalent oxidation states of carbon, trityl and xanthyl systems are atypical models for comparing transmission of electron demand In other series of carbocations, radicals or carbanions with significantly different structures. The 9-arylxanthyl series is especially poor because of its insensitivity to substituent effects. The effects of substituents on various properties which represent the stabilities of R(+)s correlate surprisingly well against those for corresponding R(-)s. Accordingly, compensating effects on the oxidation and reduction of a series of related RS may lead to a nearly constant electron transfer energy and absolute hardness for the series. In contrast, the free energies for interconversion of the carbocations and carbanions which determine the gap between pK(R+) and pK(HA) are very sensitive to structural change. (C) 1997 by John Wiley & Sons, Ltd.
A sensitive method for identifying red blood cell antigens or antibodies thereto is provided. A fluorescent bead is conjugated to a receptor specific for a red blood cell antigen (ligand) or alternatively with an antigen for determination of antibodies. The conjugate is mixed with a red blood cell containing composition. A change in fluorescence compared with a control reveals the presence or absence of the antigen or antibody.
Method and apparatus for enhanced detection of electromagnetic signals
申请人:SYNTEX (U.S.A.) INC.
公开号:EP0155813A2
公开(公告)日:1985-09-25
A beam of incident electromagnetic radiation is generated having a spatial distribution of intensity periodically varying in time. A receiver suspected of containing an analyte is irradiated with the beam, and the electromagnetic signal emitted is detected and the correlation, if any, is determined between the periodicity of the applied beam and fluctuations in the detected signal. The method and apparatus have particular applicability in the field of particle detection, e.g. fluorescent particle detection.
A fluid handling system is described wherein a small fluid volume (16) is placed on a reversibly-deformable support (12), which can be deformed to form a cavity. As the fluid clings to the surface of the support, it is physically agitated and mixed as the support is deformed. The deformable support can be utilized to provide fluid containers of varying sizes, to accommodate different fluid volumes and as a transport mechanism to move fluid from one location to another.
Apparatus and method for detection of fluorescence or light scatter
申请人:SYNTEX (U.S.A.) INC.
公开号:EP0335725A2
公开(公告)日:1989-10-04
An apparatus and method are described for defining a small interrogation volume in a liquid sample suspected of containing an analyte. The apparatus and method utilize a dual optical fibre probe (10) constructed with the ends of the optical fibres (12,14) at the liquid/fibre interface spatially oriented such that the intersection of their longitudinal axes forms an included angle ranging from about 40° to 140°. By appropriate choice of the numerical aperture and core diameter of the optical fibres and the separation distance between the longitudinal axes of the optical fibres at the liquid/fibre interface, a finite interrogation volume of predetermined size and independent of the total liquid sample volume can be defined. The apparatus and method substantially reduce background interference with corresponding increase in assay sensitivity.