Abstract

An instrument to measure the excited-state lifetimes of phosphorescent materials in real time is described. This apparatus uses pulsed and frequency-doubled Nd:YAG solid-state laser for excitation, sampler for data acquisition, and frequency domain methods for data fitting. The instrument amplifies the ac components of the detector output and band limits the signal to 25 kHz. The fundamental frequency of the excitation is then set to obtain a desired number of harmonics. This band limited signal is sampled and averaged over few thousand cycles in the time domain. The frequency domain representation of the data is obtained by employing fast Fourier transform algorithms. The phase delay and the modulation ratio of each sampled harmonic is then computed. Ten to a hundred values of the phase and modulations are averaged before computing the sensor lifetime. The instrument is capable of measuring precise and accurate excited-state lifetimes from subpicowatt luminescent signals in 100 μm optical fibers. To monitor oxygen for biomedical applications the response time of the system is decreased by collecting only 8 or 16 harmonics. A least-squares fit yields the lifetimes of single exponentials. A component of zero lifetime is introduced to account for the backscatter excitation. The phosphorescence lifetimes measured reproducibly to three parts in a thousand are used to monitor oxygen. Oxygen concentrations are computed employing empirical polynomials. The system drift is less than 1% over 100 h of continuous operation. This instrument is used to measure oxygen concentrations in vitro and in vivo with 2 s update times and 90 s full response times. Examples of measurements in saline solutions and in dogs are presented.

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