A series of 2'-arylbenzaldehyde oxime ethers were synthesized and shown to generate the corresponding phenanthridines upon irradiation in the presence of 9,10-dicyanoanthracene in acetonitrile. Mechanistic studies suggest that the oxidative cyclization reaction sequence is initiated by an electron transfer step followed by nucleophilic attack of the aryl ring onto the nitrogen of the oxime ether. A concave downward Hammett plot is presumably the result of a change in charge distribution in the radical cation species with strongly electron-donating substituents that yields a less electrophilic nitrogen atom and a decreased amount of cyclized product.
View Article and Find Full Text PDFA significant advantage of a graphene biosensor is that it inherently represents a continuum of independent and aligned sensor-units. We demonstrate a nanoscale version of a micro-physiometer - a device that measures cellular metabolic activity from the local acidification rate. Graphene functions as a matrix of independent pH sensors enabling subcellular detection of proton excretion.
View Article and Find Full Text PDFIt is widely recognized that an array of addressable sensors can be multiplexed for the label-free detection of a library of analytes. However, such arrays have useful properties that emerge from the ensemble, even when monofunctionalized. As examples, we show that an array of nanosensors can estimate the mean and variance of the observed dissociation constant (KD), using three different examples of binding IgG with Protein A as the recognition site, including polyclonal human IgG (KD μ = 19 μM, σ(2) = 1000 mM(2)), murine IgG (KD μ = 4.
View Article and Find Full Text PDF