ABSTRACT
In the standard NMR spectra, the lineshape patterns produced by a molecular rate process are often poorly structured. When alternative theoretical models of such a process are to be compared, even quantitative lineshape fits may then give inconclusive results. A detailed description is presented of an approach involving fits of the competing models to series of Carr-Purcell echo spectra. Its high discriminative power has already been exploited in a number of cases of practical significance. An explanation is given why it can be superior to methods based on the standard spectra. Its applicability in practice is now illustrated on example of the methyl proton spectra in 1,2,3,4-tetrachloro-9,10-dimethyltriptycene TCDMT. It is shown that, in the echo spectra, the recently discovered effect of nonclassical stochastic reorientation of the methyl group can be identified clearly while it is practically nondiscernible in the standard spectra of TCDMT. This is the first detection of the effect at temperatures above 200 K. It is also shown that in computer-assisted interpretation of exchange-broadened echo spectra, the usual description of the stimulating radiofrequency pulses in terms of rotation operators ought to be replaced by a more realistic pulse model.
ABSTRACT
The binding of dimethyldiazaperopyrenium dication (1) with nucleosides, nucleotides, and single-stranded polynucleotides has been studied by photophysical methods. It has been shown that 1 may be a potential selective fluorescent probe for A- and/or T-rich polynucleotides. 1 efficiently cleaves oligonucleotides at guanine sites, under illumination with visible light, and therefore may be used as a sequence-specific artificial photonuclease.
