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Default unusual tyrosine cross peaks

unusual tyrosine cross peaks

Hi I am observing some unexpected cross peaks in some homonuclear protein data and I was wanting to know if anyone had an ideas what im looking at. I am looking at what I was confident was a tyrosine HE-HD cross peak in a TOCSY giving charachterticaly intense cross peaks at 6.9 x 6.4 ppm, however I then noticed a second set of TOCSY peaks to both the HE* and HD* at 5.4 ppm which also gives a COSY to the HE. These peaks shift together if I change the temperature sugesting it is not just two overlaped resonances, are still present in D2O, both the HE and HD* give the anticipated intensity in the 1D sugesting theses are not chemical exchange cross peaks. my initial gues was observation og the Tyr OH but the chemical shift doesnt really make sense and one wouldnt expect to see a COSY to the OH either, this is not ovrlaped with an NH2 or NH (by compsrison with my HSQC) any ideas, im at a bit of a loss and not sure if im just not missing an obvious explanation.Any help would be apreciatedTom



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