One and two dimensional H-1-NMR experiments have been performed to study the molecular order and dynamics of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) unilamellar vesicles under the influence of high pressure and the local anesthetic, tetracaine (TTC), which can also be considered as a model-charged amphiphile. The TTC molecules have an ordering effect on the headgroups but a disordering effect on the acyl chains, whereas, pressure has an ordering effect on the acyl chains. The results from 2D NOESY experiments on pure DPPC vesicles show that the intensities of NMe(3)/CH3, NMe(3)/(CH2)(n) and CH3/(CH2)(n) cross-peaks increase with increasing pressure in the liquid-crystalline phase but decrease with pressure in the gel phase, further suggesting that the appearance of the cross-peaks between the two extremes of the DPPC molecules is due to spin-diffusion. For the DPPC/TTC vesicles, the 2D NOESY experiments confirm that charged TTC molecules are located in the headgroup region of the DPPC bilayers and, in the gel phase, also suggest the formation of an interdigitated gel phase.