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th  - 1988 - 51st ENC Conference

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192 RESOLUTION ENHANCEMENT OF PHOSPHORUS-31 SPECTRA<br />

I<br />

THE USE OF CDTA IN PERCHLORIC ACID EXTRACTS OF DICTYOSTELIUM DISCOIDEUM<br />

Kenne<strong>th</strong> L. Williamson* and E<strong>th</strong>el F. Fromm*<br />

Department of Chemistry, Mount Holyoke College, Sou<strong>th</strong> Hadley, MA 01075<br />

Dramatic increases in resolution of 31p spectra have been found in<br />

perchloric acid extracts of <strong>th</strong>e cellular slime mold, Dictyostelium discoideum,<br />

by using CDTA (trans-l,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid<br />

hydrate) in place of <strong>th</strong>e traditional EDTA (e<strong>th</strong>ylenediaminetetraacetic acid) to<br />

L 193<br />

complex wi<strong>th</strong> cations. These high resolution spectra have been used to study<br />

<strong>th</strong>e phosphorus metabolism of D, discoideum during all stages of its<br />

development during <strong>th</strong>e 24 hr time period in which it undergoes, under<br />

conditions of starvation, development from single-celled amoebae to a<br />

multicellular organism containing stalk cells and spores. The present study<br />

has focused on <strong>th</strong>e latter part of <strong>th</strong>e developmental process.<br />

IADDITIVITY OF CARBON-13 SPIN-LATTICE RELAXATION TIMES IN OCTENES<br />

Kenne<strong>th</strong> L. Williamson*, Maureen A. Simonds* and Thomas R. Stengle<br />

*Department of Chemistry, Mount Holyoke College, Sou<strong>th</strong> Hadley, MA 01075<br />

Department of Chemistry, University of Massachusetts, Amherst, MA 01003.<br />

Carbon-13 spin lattice relaxation times have been measured for a number of<br />

isomeric octenes in order to explore <strong>th</strong>e relationships between T I and<br />

molecular dynamics and conformations. Systematic trends were observed in <strong>th</strong>e<br />

relaxation times so <strong>th</strong>at an empirical relationship could be derived which<br />

allows one to estimate <strong>th</strong>e T I of a given carbon atom by summing additivity<br />

parameters based on <strong>th</strong>e location of <strong>th</strong>e given carbon relative to <strong>th</strong>e double<br />

bond, to me<strong>th</strong>yl groups, and to centers of branching. These additivity<br />

parameters were obtained by performing a linear multiple regression analysis<br />

on <strong>th</strong>e Tl'S of individual carbons in <strong>th</strong>e octenes. The T I of a given carbon<br />

atom can <strong>th</strong>en be derived by simply summing appropriate combinations of<br />

regression coefficients in exactly <strong>th</strong>e same way <strong>th</strong>at 13C chemical shifts can<br />

be calculated.<br />

195

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