PubMed · 1750928
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H E Mattox, J E Richter. 1991. Manometry vs. pH step-up.. https://pubmed.ncbi.nlm.nih.gov/1750928/
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[reaction: see text] N-Acyliminium cation of prolines was efficiently generated to accumulate in an undivided cell at 0 degrees C by an anodic oxidation of N-acylprolines or alpha'-phenylsulfanylated N-acylproline derivatives in a lithium perchlorate/nitromethane solution. The iminium cation intermediates gave modified prolines by a reaction with nucleophiles under mild conditions.
Groups of fibres rather than single afferents may be responsible for encoding various intensity aspects of tactile skin stimulation. Reconstruction of population responses of primary afferent fibres to skin displacement provided data in support of this idea, but evidence from direct recordings that demonstrated multifibre activity deriving from groups of single units firing in response to defined skin stimuli were not reported. Procedures are summarised which allow identification and sampling of such recordings in man. For SAII units it was demonstrated how different directions of skin stretch engaging a particular cutaneous area produced different responses of a unit population innervating that site. In response to localised vibratory stimuli synchronous discharges of several co-activated PC afferents were recorded at each vibratory cycle, which is a previously not described pattern of peripheral PC encoding. Population projection of activity within modality segregated clusters of afferents supplying the same skin area might serve as basic projection units and constitute the peripheral counterparts to sensory columns, believed to be the central cognitive correlates, in the cortex. Thus, it is tempting to postulate fibre population projection as a peripheral basis for somatosensory processing in man.
An anodic cyclization reaction between an enol ether radical cation and an oxygen nucleophile has been used to make a tetrahydropyran building block for the C(10)-C(16) portion of bryostatin. The oxidative cyclization was successful despite the presence of a thioacetal group that has a lower oxidation potential than the enol ether. Experimental evidence suggested that the reaction proceeded through an initial oxidation of the thioacetal followed by an intramolecular electron transfer to form the enol ether radical cation that was subsequently trapped by the oxygen nucleophile. The formation of the desired cyclic product could be explained using the Curtin-Hammett principle. By taking advantage of the intramolecular electron-transfer reaction, we used the presence of a thioacetal in an electrolysis substrate to selectively oxidize a proximal enol ether in the presence of an otherwise identical but more remote enol ether.