Reagents. Tetrahydrofuran and triethylamine (EMD) were dried using solvent purification columns, and the final water content was monitored by Karl Fisher titration. 26 Ethanol and acetonitrile (EMD) were distilled from sodium metal and stored over molecular sieves (4Å) before use. Dichloromethane (EMD), methanol (EMD), hexanes (EMD), ethyl acetate (EMD), alanine ethyl ester hydrochloride (Chem Impex), phenylalanine ethyl ester hydrochloride (Chem Impex), sodium (Sigma), tyramine (TCI), ditert butyl dicarbonate (Sigma), sodium bicarbonate (Sigma), diethyl vinylphosphonate (TCI), ferulic acid (Sigma), trifluoroacetic acid (Sigma), sodium iodide (Aldrich), and trimethylsilyl chloride (Fluka) were used as received. Spectra/Por molecular porous cellulose dialysis membranes with a molecular weight cutoff of 12,000-14,000 were used for purification of the polymers.Equipment. 31 P and 1 H NMR spectra were obtained with a Bruker 360 WM instrument operated at 145 MHz and 360 MHz, respectively. 31 P shifts are reported in ppm relative to 85% H 3 PO 4 at 0 ppm. Glass transition temperatures were measured with a TA Instruments Q10 differential scanning calorimetry apparatus with a heating rate of 10 °C/min and a sample size of ca. 10 mg. Gel permeation chromatography was performed using a Hewlett-Packard 1047A refractive index detector and two Phenomenex Phenogel linear 10 columns. The samples were eluted at 1.0 mL/min with a 10 mM solution of tetra-n-butylammonium nitrate in THF. The elution times were calibrated with polystyrene standards. Mass spectrometric analyses were performed using a Waters LCT Premier time-of-flight (TOF) mass spectrometer in positive or negative ion mode, using electrospray ionization (ESI). Ultraviolet spectra were obtained with a double-beam spectrophotometer (Varian, Cary 500). Measurements were conducted in de-ionized water or in a 10 mM phosphate buffered saline solution (PBS).
Synthesis of bis-(diethyl phosphonate)-N,N-diethyltyramine (DPT) and (diethyl phosphonate)-Nethyltyramine (MPT).Tyramine (1.73 g, 12.6 mmol) and diethylvinylphosphonate (3.60 g, 21.9 mmol) were dissolved in de-ionized water (160 mL) and heated at 50 °C for 48 h. The sample was cooled and extracted with DCM. The organic layers were combined and dried over magnesium sulfate. Once dry, the solvent was removed under reduced pressure and dried further under vacuum to afford the product as a crude oil. The