PHENOXY RADICAL DETECTION
31P NMR spectra
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31P NMR spectra were acquired on a Bruker-300 spectrometer
(operating at 121.49 MHz). The chemical shifts reported are
relative to external orthophosphoric acid (85%). All spectra were
acquired with proton decoupling. The total number of scans for
all experiments was 256–1024 with an acquisition time of 1.60 s.
Trimethylphosphate was used as the internal standard for
quantification and was added to the sample prior to measure-
ment. The relaxation time (T1) of the internal standard was
measured and was determined to be approximately 13.5 s. In
order to decrease the relaxation time, a relaxation agent
(chromium chloride or chromium acetylacetonate) was added
to the mixture. With the addition of relaxation agent
(30–35 mmol/L) to the samples prior to NMR measurement,
the relaxation time of the phosphorus nuclei was decreased to
200 ms. 5T1 was used for the pulse delay.
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Freeze-dried samples were solubilized in about 10 mL of hexane.
Structural analyses were performed by injecting 2 mL of the
extracted sample in a Hewlett Packard 5972 mass spectrometer
(EI 70 eV) interfaced to a Hewlett Packard 5890-A gas chromato-
graph. Chromatographic separation was performed using a DB-5
30 mꢀ0.25 mm fused silica capillary column (J. and W. Scientific
Agilent Technologies). Chromatographic conditions: initial
temperature 60 8C, 2 min isothermal, 10 8C/min up to 200 8C,
6 8C/min up to 280 8C, 20 min isothermal. Carrier gas: He (purity
99.995%), constant flow 1.0 mL/min.
¨
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