Supplementary MaterialsSupllemental. nitrogen atmosphere. For the iodine-substituted derivative, BF2dnm(I)PLA, obviously distinguishable fluorescence (green) and phosphorescence (orange) peaks are present, making it ideal for ratiometric oxygen-sensing and imaging. Bromide and hydrogen analogues with weaker relative phosphorescence intensities and longer phosphorescence lifetimes can be used as highly sensitive, concentration impartial, lifetime-based oxygen sensors or for gated emission detection. BF2dnm(I)PLA nanoparticles were taken up by T41 mouse mammary cells and successfully demonstrated differences ratiometric measurement of oxygen. immediately before measurements were taken. Polymers were fabricated into nanoparticles by previously explained methods.55 Nanoparticle size was determined by dynamic light scattering (DLS) on a Wyatt Corporation DynaPro Plate Reader II. Ratiometric oxygen sensitivity calibration is performed as previously explained.58 Images of films and nanoparticles were taken with a Canon EOS 7D camera with handheld UV lamp excitation (ex = 354 nm). 1-[6-(2-Hydroxyethoxy)-2-napthyl]-3-(2-naphthyl)-propane-1,3-dione (dnmOH) (1) The aromatic ketone, 1-(6-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)naphthalen-2-yl)ethanone was prepared as previously explained.33 1-(6-(2-((Tetrahydro-2H-pyran-2-yl)oxy)ethoxy)naphthalen-2-yl)ethanone (740 mg, 2.35 mmol) and methyl 2-naphthoate (526 mg, 2.82 mmol) were weighed in a dry 100 mL round-bottom flask and dissolved in anhydrous THF (~ 20 mL). A suspension of anhydrous THF (~10 mL) and NaH (85 mg, 3.5 mmol) was transferred to the flask via cannula. The reaction mixture was heated at 60 C and monitored by TLC until the limiting reagent (ketone) was consumed. After 1 d, the reaction combination was cooled to room heat and quenched by drop-wise addition of saturated NaHCO3 (aq) (10 mL). THF was removed by rotary evaporation and the remaining aqueous layer was acidified with 1M HCl and extracted with CH2Cl2 (2 100 mL). The combined organic layers were washed with distilled water (2 100 mL) and brine (2 100 mL), dried RAC3 over Na2SO4 then, filtered, and focused in vacuo. The causing brown, greasy residue was dissolved in THF (50 mL) buy INK 128 and drinking water (15 mL), and p-TsOH (50 mg, 0.29 mmol) was added. The reation mix was warmed at 60 C and supervised by TLC. After 18 h, the response mix was cooled to area heat range and THF was taken out by rotary evaporation. The causing residue was dissolved in CH2Cl2, cleaned with distilled drinking water (2 100 mL), brine (2 100 mL), and dried out over anhydrous Na2SO4. The answer was filtered, and solvent was taken out via rotary evaporation. The tan shaded crude item was purified via recrystallization with 1:1 hexanes/EtOAc to provide 1 being a tan natural powder: 490 mg (54%). 1H NMR (300 MHz, CDCl3): 17.12 (s, 1H, -OH), 8.58 (s, 1H, 1-ArH), 8.53 (s, 1H, 1-ArH), 8.08 (d, J = 3.0, 1H, buy INK 128 8-ArH), 8.05 (d, J buy INK 128 = 3.0, 1H, 8-ArH), 8.01 (d, J = 7.2, 1H, 4-ArH), 7.95-7.89 (m, 3H, 4-ArH, 3-,5-ArH), 7.83 (d, J = 8.7, 1H, 3-ArH), 7.59 (m, broad, 2H, 6-, 7-ArH), 7.26 (d, J = 8.7, 1H, 7-ArH), 7.21 (s, 1H, 5-ArH), 7.13 (s, 1H, -COCHCO), 4.35 (t, J = 4.2, 2H, -ArOCH2CH2OH), 4.09-4.05 (m, 2H, -ArOCH2CH2OH), 2.05 (s, 1H, -ArOCH2CH2OH). HRMS (ESI, TOF) m/z calcd for C25H21O4 385.1440 [M + H]+; present 385.1433. 1-[6-(2-Hydroxyethoxy)-2-napthyl]-3-(6-bromo-2-naphthyl)-propane-1,3-dione (dnm(Br)OH) (2) The bromine derivative was ready as defined for 1 using methyl 6-bromo 2-naphthoate rather than methyl 2-naphthoate. A tan natural powder was attained: 340 mg (46%). 1H NMR (300 MHz, (Compact disc3)2SO): 17.34 (s, 1H, -O3, 4-Arcalcd for C25H20O4Br 463.0545 [M + H]+; present 463.0538. 1-[6-(2-Hydroxyethoxy)-2-napthyl]-3-(6-iodo-2-naphthyl)-propane-1,3-dione (dnm(I)OH) (3) The iodine derivative was ready as previously defined for 1 with methyl 6-iodo 2-naphthoate rather than methyl 2-naphthoate. The crude dnm(I)OH item 3 was buy INK 128 purified by recrystallization with acetone rather than hexanes/EtOAc to produce a tan natural powder: 98 mg (11%). 1H buy INK 128 NMR (300 MHz, (Compact disc3)2SO):.