RESUMEN
Herein we report the synthesis, isolation and polymerisation activity of two new zinc compounds based on a 2,6-diisopropylphenyl (Dipp) ß-diiminate (NacNac) ligand framework with zinc also ligated by an amidate (2-pyridonate or 6-methyl-2-pyridonate) unit. The compounds crystallised as either monomeric (6-Me-2-pyridonate derivative) or dimeric (2-pyridonate) species, although both were found to be monomeric in solution via1H DOSY NMR spectroscopy, which was supported by DFT calculations. These observations suggest that both complexes initiate ring-opening polymerisation (ROP) through a single-site monometallic mechanism. High molecular weight poly ε-caprolactone (PCL) was achieved via exogenous initiator-free ROP conditions with both catalysts. An increase in the 2-pyridonate initiator steric bulk (6-Me- vs. 6-H-) resulted in an improved catalytic activity, facilitating complete monomer conversion within 1 h at 60 °C. Pyridonate end-groups were observed by MALDI-ToF mass spectrometry, contrasting with previous observations for DippNacNac-Zn acetate complexes (where no acetate end groups are observed), instead this more closely resembles the reactivity of DippNacNac-Zn alkoxide complexes in ROP (where RO end groups are observed). Additional major signals in the MALDI-ToF spectra were consistent with cyclic PCL species, which are attributed to back-biting ring-closing termination steps occuring in a process facilitated by the pyridonate unit being an effective leaving group. To the best of our knowledge, these complexes represent the first examples of pyridonate, and indeed amidate, initated ROP.
RESUMEN
For application in a portable transdermal drug-delivery system, novel transducers have been designed to enhance insulin transmission across skin using ultrasound. Previous research has shown transdermal delivery of insulin across skin using commercial sonicators operating at 20 kHz with intensities ranging from 12.5 to 225 mW/cm2. The goal of this research was to design and construct a small, lightweight transducer or array that could operate with a similar frequency and intensity range as a commercial sonicator used in previous transdermal ultrasound insulin experiments, but without the weight and mass of a sonicator probe. To obtain this intensity range, a cymbal transducer design was chosen because of its light, compact structure and low resonance frequency in water. To increase the spatial ultrasound field for drug delivery across skin, two arrays, each comprising of four cymbal transducers, were constructed. The first array, designated the standard array, used four cymbals transducer elements in parallel. A second array (named the stack array) used four cymbal transducers that used stacked piezoelectric discs to drive the titanium flextensional caps. Under similar driving conditions, the standard array produced intensities comparable to those achieved using a commercial sonicator.